Nonlinear optical materials containing polar disulfone-functionalized molecules

Nonlinear optical (NLO) compositions are disclosed which contain polar disulfone-functionalized molecules (PDFMs) incorporated in a polymeric material. when aligned noncentrosymmetrically in the polymeric material, the PDFMs generate a second-order NLO response. There is also disclosed: a method of preparing a NLO composition; novel PDFMs and novel polymers; and a new process for preparing PDFMs.

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Claims

1. Polar disulfone-functionalized molecules selected from the group consisting of:

(a) compounds of the Formula I: ##STR82## where n is 0, 1 or 2; Z independently represents an aryl group that is substituted with an electron-donating group, an activated heterocyclic aromatic group, a group derived from a dye base, or a group derived from a dye olefin; R.sup.1 and R.sup.2 each independently represent hydrogen, an alkyl group of about 1 to 4 carbon atoms, or taken together in conjunction with the catenary carbon atoms therebetween form a 5 or 6-membered carbocyclic or heterocyclic ring, when n is 2, R.sup.1 and R.sup.2, R.sup.1 and R.sup.1, or R.sup.2 and R.sup.2 may form the 5 or 6-membered carbocyclic or heterocyclic ring in conjunction with the catenary carbon atoms therebetween; and R.sub.f.sup.1 and R.sub.f.sup.2 taken together combine in conjunction with the disulfone group to form a 5, 6, or 7-membered ring containing two, three, or four carbon atoms respectively that are fluorinated;
(b) compounds of the Formula I, where n, R.sup.1 and R.sup.2, and Z are as defined above, and R.sub.f.sup.1 and R.sub.f.sup.2 independently represent fluorine, a saturated fluorinated alkyl group containing 1 to 10 carbon atoms, or taken together in conjunction with the disulfone group form a 5, 6, 7-membered ring containing 2, 3, or 4 carbon atoms, respectively, which are fluorinated, with the provisos that (i) at least one of R.sub.f.sup.1 and R.sub.f.sup.2 are fluorine, and (ii) n is 1 or 2 when Z is of the Formula II ##STR83## where Y is --NR.sup.3 R.sup.4, R.sup.3 O--, or R.sup.3 S--; Ar-- represents a monovalent aryl group having 6 to 10 ring atoms; X represents a monovalent substituent group having 1 to about 20 atoms; k is 1 or 2; m is an integer of 0 to 6; and R.sup.3 and R.sup.4 independently represent a monovalent alkyl group of 1 to 12 carbon atoms, a cyanoalkyl group of 1 to 4 carbon atoms, an aryl, alkaryl, or arylene group having 6 to 10 ring atoms and less than about 15 total carbon atoms, an alkylene, alkyleneoxy, alkylene-tert-amino, or alkylenethio group 1 to 3 carbon atoms, an alkyleneacylamino group having 1 to 3 ring atoms, an aralkyl group of up to about 15 total carbon atoms, or R.sup.3 and R.sup.4 taken together in conjunction with the nitrogen atom form one or more 5 or 6-membered heterocyclic rings;
(c) compounds of the Formula VII: ##STR84## where n is of 0, 1, or 2; R.sup.1 and R.sup.2, are as defined above; R.sup.8 represents hydrogen or a monovalent organic radical; R.sup.9 represents a monovalent organic acyl, allyl, aryl, alkyl, or aralkyl radical; and where R.sub.f.sup.1 and R.sub.f.sup.2 here represents a saturated fluorinated alkyl radical containing 1 to 10 carbon atoms, or together in conjunction with the disulfone group form a 5, 6, or 7-membered ring containing 2, 3, or 4 carbon atoms, respectively, which are fluorinated;
(d) compounds of the formula VIII: ##STR85## where R.sub.f.sup.1 and R.sub.f.sup.2 here each independently represent fluorine, a saturated fluorinated alkyl radical containing 1 to 10 carbon atoms, or together in conjunction with the disulfone group form a 5, 6, or 7-membered ring containing 2, 3, or 4 carbon atoms, respectively, which are fluorinated, and R.sup.10 is selected from the group consisting of: ##STR86## where n here is 0, 1, or 2, and R.sup.5 represents a substituent containing up to about twenty carbon atoms; and
the group derived from a dye base of Z is represented by the Formula IV ##STR90## where p is 0, or 1; R.sup.5 is as defined above; and W represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 or 6 atoms in the heterocyclic ring; and
the group derived from the dye olefin is represented by the Formula V ##STR91## where Ar, Y, X, and m are as defined above, Ar' independently represents Ar, X' and Y' independently represent X and Y, respectively, m' independently represents m, and h and h' independently represents 0, 1, or 2, with the proviso that both h and h' cannot be 0.

2. The polar disulfone functionalized molecules of claim 1, wherein the carbon atoms of at least one of R.sub.f.sup.1 and R.sub.f.sup.2 adjacent and next adjacent to the --SO.sub.2 -- groups are perfluorinated.

3. The polar disulfone functionalized molecules of claim 1, wherein at least one of R.sub.f.sup.1 and R.sub.f.sup.2 is perfluorinated.

4. The polar disulfone functionalized molecules of claim 1, wherein R.sub.f.sup.1 and R.sub.f.sup.2 are both CF.sub.3 for compounds (a), (c), and (d), and at least one of R.sub.f.sup.1 and R.sub.f.sup.2 is CF.sub.3 for compounds (b).

5. The polar disulfone functionalized molecules of claim 1, wherein:

the aryl group substituted with an electron-donating group of Z is represented by the Formula ##STR92## where Ar-- represents a monovalent aryl group having 6 to 10 ring atoms; Y represents an electron-donating substituent group having up to about 20 atoms; X represents a monovalent substituent group having 1 to about 20 atoms; k is 1 or 2; and m is an integer of 0 to 6.

6. The polar disulfone-functionalized molecules of claim 1, wherein

Y and Y' independently are an amino group of the formula R.sup.3 R.sup.4 N-- or an ether or thio group of the formula R.sup.3 O-- or R.sup.3 S--, where R.sup.3 and R.sup.4 independently represent a monovalent alkyl group of 1 to 12 carbon atoms, a cyanoaklyl group of 1 to 4 carbon atoms, an aryl, alkaryl, or arylene group having 6 to 10 ring atoms and less than about 15 total carbon atoms, an alkylene, alkyleneoxy, alkylene-tert-amino, or alkylenethio group 1 to 3 carbon atoms, an alkyleneacylamino group having 1 to 3 ring atoms, an aralkyl group of up to about 15 total carbon atoms, or R.sup.3 and R.sup.4 taken together in conjunction with the nitrogen atom form one or more 5 or 6-membered heterocyclic rings;
E is NR.sup.5, where R.sup.5 represents a substituent containing up to twenty carbon atoms; and
X and X' independently are a halo, a substituted or unsubstituted aryl group Ar-- as defined above, a lower alkyl or a substituted lower alkyl having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, a haloalkyl having from 1 to 4 carbon atoms, an acyloxy group having from 1 to 4 carbon atoms, an acylamido having from 1 to 10 carbon atoms, saturated cyclics or heterocyclics having from 3 to 10 carbon atoms, an alkylthio group having from 1 to 10 carbon atoms, an aryl or substituted aryl group having 6 to 10 ring atoms, an aralkyl group having from 7 to 15 carbon atoms, an alkenyl having 2 to 15 carbon atoms, or an aralkenyl having from 8 to 15 carbon atoms.
Referenced Cited
U.S. Patent Documents
3917714 November 1975 Richmond
3932526 January 13, 1976 Koshar
3933914 January 20, 1976 Coles et al.
3984357 October 5, 1976 Koshar
4069233 January 17, 1978 Koshar
4156696 May 29, 1979 Koshar
4357405 November 2, 1982 Leichter et al.
4859876 August 22, 1989 Dirk et al.
4973429 November 27, 1990 Decher et al.
5006729 April 9, 1991 Meijer et al.
Foreign Patent Documents
0 218 938 April 1987 EPX
0 396 172 A1 November 1990 EPX
Other references
  • Fild et al., Chemical Abstracts 110: 135357, Abstract of Chem.--ZTG. (1988), 112 (3), pp. 107-108. I.I. Malentina et al., Inst. Org. Chem., Acad. Sci. Ukranian SSR, Plenum Publishing (1980) (translated from Zhurnal Organicheskoi Khimii, v. 15, n. 11, pp. 2416-2417 (Nov. 1979)).
Patent History
Patent number: 5676884
Type: Grant
Filed: Nov 20, 1996
Date of Patent: Oct 14, 1997
Assignee: Minnesota Mining and Manufacturing Company (St. Paul, MN)
Inventors: George V. Tiers (St. Paul, MN), Robert J. Koshar (Sun City West, AZ), Louis M. Leichter (Mendota Heights, MN)
Primary Examiner: Philip Tucker
Attorney: Karl G. Hanson
Application Number: 8/752,777
Classifications
Current U.S. Class: Light Transmission Modifying Compositions (252/582); 1,4-oxazines (544/98); Sulfur Attached Directly Or Indirectly To Morpholine Ring By Nonionic Bonding (544/158); Ring Nitrogen Is Shared By Two Of The Cyclos (546/94); Benzo(a)quinolizines (including Hydrogenated) (546/95); Single Bond Between 1,2-positions And Single Bond Between 3,4-positions (546/165); The Six-membered Hetero Ring Is Unsubstituted Or Alkyl Substituted Only (546/166); Acyclic Sulfur Bonded Directly To Oxygen And Directly Or Indirectly To The Quinoline Ring System By Nonionic Bonding (546/172); Halogen Or Nitro Attached Directly Or Indirectly To The Quinoline Ring System By Nonionic Bonding (546/180); The Additional Ring Is A Hetero Ring (546/207); The Additional Hetero Ring Consists Of One Sulfur And Four Carbons (546/212); Chalcogen Attached Indirectly To The Bicyclo Ring System By Nonionic Bonding (548/179); Tetracyclo Ring System Having The Five-membered Hetero Ring As One Of The Cyclos (548/420); The Bicyclo Ring System Consists Of The Five-membered Hetero Ring And A Benzene Ring (e.g., Indole, Etc.) (548/469); Chalcogen Or Nitrogen Attached Indirectly To The Five-membered Hetero Ring By Acyclic Nonionic Bonding (548/491); Chalcogen Attached Indirectly To The Bicyclo Ring System By Acyclic Nonionic Bonding (548/509); Additional Hetero Ring, Which Is Attached Directly Or Indirectly To The Five-membered Hetero Ring By Nonionic Bonding (548/517); Chalcogen Attached Indirectly To The Five-membered Hetero Ring By Acyclic Nonionic Bonding (548/562); Chalcogen Or Nitrogen Attached Directly To The Hetero Ring By Nonionic Bonding (549/21); Chalcogen Attached Indirectly To The Hetero Ring By Nonionic Bonding (549/427); Benzene Ring Containing (568/25); Plural Halogens Containing (568/35)
International Classification: F21V 900; C07C31500;